DE1794361C2 - Polymers of Propylene or Butene-1. Eliminated from: 1494168 - Google Patents

Description

HHHHHHH _10, on the other hand, proved in the R 'and R "cone

11 11 I I! hydrogen residues, especially alkyl residues, and R '"

-CC ⁺ -CC ^ -CC ⁺ -C - a hydrocarbon residue, hydrogen, halogen

(j IJ (j I or an alkoxy group, especially AIu-

HR HR HR H miniumtriäthy! or dietary aluminum chloride.

This makes particularly active catalysts

have, in which the radicals R methyl or ethyl obtained that one are finely divided mixtures or radicals and in which the asymmetric carbon solutions of both catalyst components in one * material atom of the main chain (C ⁺ ) brings together at least for inert solvents.

Long stretches of the molecule have the same steric effect. A particularly active catalyst is obtained

Have configuration. > o furthermore, if one uses the catalyst in the presence of a

2. Polypropylene according to claim 1, characterized in that olefin, preferably in the presence of the polymer to be polymerized, produces a sizing olefin in the crystalline state, in particular in a high concentration spiral structure of the main chain with a tration, in the liquid phase. Identity period along the chain of 6.4 Å. The polymerization takes place at temperatures between

3. Polymers of propylene according to claim 1, as see 20 and 120 ° C, preferably between 50 and characterized in that, while maintaining 100 ° C, and pressures of 1 to 30 atmospheres, the crystalline structure of the propylene homo- although you can also work in a vacuum, polymeric small amounts of copolymerized In general, it is advisable to use the olefins in the Contains ethylene. polymerize liquid phase, d. H. either the

30 liquid olefins as such or gaseous' or liquid olefins in solution with inert solution

to use funds. The polymerization products obtained are treated with water or alcohol, to decompose the organometallic compounds

The invention relates to polymers of the Pro- 35 and then optionally washed with acids, pyiens or butene-1. around the metal compounds formed during decomposition

These new polymers are marked to dissolve fertilizers. Products are obtained with a high nei; that they have linear and essentially unbranched molecular weights, which are essentially different from the Prosind a head-to-tail concatenation, a products that differ according to known methods average molecular weight greater than 4 »from asymmetric free radical olefins 20,000 and a structure corresponding to the formula can be obtained as catalysts.

The polymer mixtures obtained exist on the one hand HHHHHHH mainly made of polyolefins with a through- Il Il Il I average molecular weight of more than 20,000,

- C - C - C - C * - C - O - C - 45 those made of macromolecules with a regular

Il Il Il I sequence of CH ₂ groups and CHR groups HRHRHRH consist in long straight chains, those of the general Structural formula

have, in which the radicals R are methyl or ethyl radicals HH HH HH

are and wherein the asymmetric carbon atoms 50 ι ι 1 ι ι ι

the main chain (C ⁺ ) at least for long distances I 'Il Il

of the molecule have the same steric configuration. -C-C '- C - C * - C - C *

The new polymers are produced by '; ; Polymerization of the olefins in the presence of Kataly- HR HR HR

by the reaction of compounds of the 55th

Metals of the subgroups IV. To Vl. Group correspond and in which the asymmetric carbon of the periodic table, including thorium material atoms of the main chain (C ⁺ ) at least for long and uranium, with organometallic compounds of the stretch of the molecule the same steric configuration metals of the 1st to IU. Group of the periodic so that the polymers obtained a significant tendency system. 60 to crystallize, and on the other hand in the

In addition to propylene, the starting material is mainly amorphous, linear, essentially Butene-1 is also a question of ethylene, from the low level of unbranched polymers of olefins with a Amounts copolymerized with propylene are greater than average molecular weights be able. 2000 in which the asymmetric carbon atoms

These olefins become static in the presence of products 65 of the two steric configurations polymerized, which by reaction of the compounds have distribution along the main chain, In the case of titanium, zirconium, hafnium, thorium, uranium and propylene polymers contain these mixtures Vanadins. Niobium, tantalum, chromium, molybdenum and in addition to the amorphous, linear, essentially un-

branched polymers with an average merizate of the higher olefins with molecular weight

Molecular weight of more than 2000 solid poly over 20,000 can according to this known method

propylene cannot be obtained with an average molecular drive,

weight of more than 20,000, consisting of macro When implementing with at the beginning

molecules with a regular sequence of S catalysts give polymerization products.

CH »groups and CH - CHj groups in long the mixtures of polymers of different steric

straight chains that are of general structural formula and various molecular weights.

"" They are broken down into fractions by solvents

«11 Ii ti it separates that contain polymers of various structures.

II 11 II 11 »o Solvents are used for separation which

-CC ⁺ -CC ^ -CCCC ⁺ the highly crystalline polymers do not swell and

i 1 Ii Il i I have boiling points below 150 ^° C. Come as such

H CH ₃ H CH _a H CHj H CH ₃ aliphatic ethers, paraffinic hydrocarbons,

for example n-heptane or iso-octane, light petrol

correspond, in which the asymmetric carbon 15 non-aromatic type or chlorinated hydrocarbons

atoms of the main chain (C ⁺ ) at least for long substances, such as carbon tetrachloride, in question.

Stretching the molecule to the same steric configuration It is mostly convenient to do this before separating the

to have. at least partially crystalline polymers the normal

The specified molecular weights were based on phen proportions of the polymerization products with Lö-

Reason of specific viscosity measurements of 30 solvents to eliminate the higher crystalline

Solutions that do not swell 0.1 g of polymer in 100 ml of tetrahydro parts to a greater extent, for example

contained naphtha, and of intrinsic viscosity with ethyl ether, isopropyl ether or tetrahydro-

measurements appreciated. Under specific viscosity furan.

one understands the difference between the viscosity as an example of such a fractionation

the solution and the viscosity of the solvent, as described in the following procedure, with the polymers

divided by the viscosity of the solvent; of propylene or mixed polymers of ethylene and

intrinsic viscosity is understood to mean the limit of propylene with a high propylene content worked up

Relationship between specific viscosity and can be. These polymerization products are Concentration for concentrations that approach zero initially treated with boiling ether. From the

converge. 30 ether extract is obtained from polypropylene, which has a

In the literature, there is no information about the weight of the certificate from more than 2000 to about 45,000 and

pylenpolyiT; er, which in the X-ray analysis has a specific viscosity below 0.12 (for solutions

appear crystalline at ordinary temperature. of 0.1 g of polypropylene in 100 ml of tetrahydronaph-

It has always been assumed that the propylene has little thalin at room temperature). This polypropylene

is capable of forming crystalline polymers. Even 35 lene are not or only slightly crystalline, and the

other ^ -olefins, which after polymerization generally have high molecular weight fractions, have viscous elastic

moderate series of asymmetric carbon properties of the unvulcanized type

containing atoms are normally not solid, even elastomers Part of the product with a special

if they are high molecular weight, and if they are solid fish viscosity of 0.106 appears on the X-ray

(Polystyrene), they are, as is well known, never crystalline. * o Radiation analysis completely amorphous. He will only

In many scientific publications it is ^{easily liquid at 135 0} C and has a density below 0.90.

aach stated that these polymers because of the The subsequent extraction is carried out with boiling

possible different steric orientations n-Kcpian and leads to products that have a molecular

of the carbon atoms of the main chain non-crystalline weight from about 45,000 to about 100,000 and one

could be. So it is said in the book »Fibers from Syη- 45 have specific viscosity over 0.12 to 0.20 and

thetic Polymers ”by Rowland Hill, Elsevier are partially crystalline. A partial product with a

Publishing Company, 1953, p. 319. has a specific viscosity of 0.121 to 0.128

“The polymers in which one of the hydrogen has an average molecular weight between 45,000

atoms of the methylene group through a methyl group and 55 000, melts at 150 C and appears at the

is substituted, are usually largely crystalline as a result of their stereoscopic so X-ray analysis,

chemical irregularity not crystalline; es The crystallinity is maintained up to over 100 ° C

come irregularly to the right and left - only to disappear completely after 150X. at

rotating groups. «Temperatures at which part of the crystallinity

In British patent 578 584 it has essentially disappeared, these products behave like

borrowed a process for making polymers 55 elastomers. Only at higher temperatures

of ethylene or copolymers of ethylene with liquid they turn into very viscous solutions

relatively small amounts of other monomers in an After the n-heptane extraction, products remain

Described essence of peroxy compounds. back, which has a molecular weight of over 100,000, Homopolymers of higher olefins, such as a specific viscosity above 0.20, melting points

for example those of propylene and n-butene-1, will have 60 over 160 ⁰ C and a high crystallinity. the

this does not include. Crystallinity is maintained up to about 150 "C.

According to Example 14 of this British patent. When this temperature is reached, the poly-

it should not be made from a large amount of ethylene and one more directly from the solid state to the liquid

a small amount of propylene, but keep it in a proportionate way

are provided, but the 6 _S wide temperature range obtained here is the properties of a

Product also just a polyethylene with a low amorphous, plastic mass. You can already Content ah propylene »as from the melting point at temperatures lower than those at which

(80 to 90 ^c C) can be seen. Kriställine Mischpoly- the crystalline structure disappears completely, only

• ■ ·

Resht at temperatures above 150 ⁰ C, slightly to the hand, the crystalline polypropylenes of the door plastics known methods, * molding or extrusion molding, and above 165 ° C isobutylenes, for example, by the known methods produced polygon, the spiral also a linear by spraying or process spiders. 'Have chain, different. The polyisobutylenes are

These high molecular weight, highly crystalline propylene 5 elastomers and have one of them different identi-

polymers have a specific gravity between 0.90 activity period.

and 0.94. The .Products with the highest density The high molecular weight polypropylenes are above

have the highest molecular weight and are deformed in the temperature range from 130 to 150 ° C

Kn. The presence of amorphous parts with low, transparent sheets are obtained if that

likes molecular weight lowers the melting point «product is well cleaned isL These leaves can be cold

and the density of the products. up to 700%, warm even further. the

The most intense and most important X-ray fracture loads, based on the cross-section of the lcn diffraction of the crystalline polypropylene de-stretched sample, values over 30 kg / mm * can increase lattice spacings of 6.2, 5.2 and 4.7 A and be even higher when the product increases 15 fine threads are drawn out between grid planes parallel to the chain axis. The stretched threads and from 4.1 A between not parallel to the axis have a silky appearance and high quality Levels. mechanical properties, especially high

The head-to-tail linkage of the molecules leaves a breaking load and a high elongation at break. she

due to their regular arrangement and they are particularly suitable for the production of textile fibers

Evidence of the crystallinity of the polymers, which is why it is so suitable. The polypropylene foils are great

by X-ray analysis. Interest in all applications where better

If one uses aluminum-mechanical properties than those of the ordinary as catalyst components

miniumtriethyl, so one finds part of the ethylene, polyethylene are necessary, especially for the Her- _{

the replacement of ethylene from the catalyst by elastic, flexible materials,

was formed by the olefin to be polymerized, »5 The described properties of the crystalline

in the polymerization products again. The largest polypropylenes are retained even when small

Part of this ethylene is due to the fact that the less crystalline changes in the structure are made Polymerization products contain, as from the small amounts of other vinyl hydrocarbons in Checking the ratio between methyl and polypropylenes are introduced or when Methylene groups in the various fractions, 30 ethylene is also polymerized,

which is also the polybutene-1 according to this invention by extraction of the polymerization product

tes obtained with solvents, by means of infrared spectrocrystalline. The temperature at which its crystalline

graph. The product provides good fiber structure disappears, but is lower than the de-

only after removal of the lower molecular speaking temperature in the case of polypropylene.

Factions. 35 Polybutene-1 also has the property of being light On the other hand, to produce the spinnable tu and in the cold stretchable threads are used Catalyst instead of triethylaluminum one with good mechanical properties, in particular Alkyl aluminum compound with alkyl groups that have high flexibility, very high tensile strength and

have more than two carbon atoms such as too elastic ductility and high elasticity as well

polymerizing olefins, polymers are obtained which provide good insulating properties. Since the poly-

the larger proportions of fractions with higher frontier butylene at lower temperatures than the poly-

have viscosity. When using an aluminum propylene it loses its crystallinity, it is with higher ones

alkyls whose alkyl groups have the same carbon temperatures and are also less dimensionally stable,

have the same number of atoms as the olefins to be polymerized, The special mechanical, elastic, chemical

one obtains polymers with the highest structural rule 45 and electrical properties of the new poly-

moderation. In the case of propylene, for example, olefins can enable their advantageous use, both

the non-fractionated, using a reac- for example as plastic masses, for production

product made of aluminum tripropyl and titanium of electrical cables and electrical insulation

nium tetrachloride as a catalyst obtained product materials or from ropes, which on the water

will be fun and results in fibers with good mcchani- 50 swim. The polypropylene and polybutene-l

see properties. according to the invention show in the oriented state

These high molecular weight, highly crystalline values of the impact strength are spun on. the linen products, so one receives threads, which are cold polymers of these A-olefins with a strong tendency to let stretch, excellent mechanical intrinsic crystallization, especially those caused by mechanical shops, and also products oriented in the textile sector, can be used by. From diffraction recordings of their interest in the production of fibers. Here stretched specimens, which show the orientation of the crystals, it is important that also copolymers from convince one can on an identity period along the weighing amounts of propylene with small amounts A chain of 6.4 Å or a multiple of this ethylene still has a certain crystallinity and intrinsic value, as well as a non-flat, probable nature of the polypropylene. It has apparently spiral structure of the paraffinic shown that polymer fibers are based on the un-main chain. This structure gives the products branched head-to-tail polymers of propylene characteristic properties which up to now for none and butene-1 in general are much better properties " Hydrocarbon were known. shafts have as fibers made of polyethylene or

The crystalline polypropylenes are not brittle 65 other hydrocarbon polymers. By name are

like the crystalline polyethylene and show these fibers made of polypropylene in several respects, both

compared to a higher elasticity, which is likely for example in terms of the specific weight, the is due to its spiral structure. And the elasticity and heat resistance of the poly-

Superior to ethylethylene fibers to an extent that could not have been foreseen.

Be i s ρ i e I 1

In a solution of 11 »4 g of triethylaluminum ii; 150 ml of petroleum ether were added 1.8 g of TiCl ₄ dissolved in 50 ml anhydrous petroleum ether (boiling point 98'G), with little below room temperature lying temperatures (5 to 10 ^c C) is added dropwise. The solution was then diluted to 500 ml and introduced into a portable stainless steel autoclave with about 21 capacity, which had previously been completely dried and evacuated. 190 g of liquid, carefully dried propylene were then pumped into the autoclave and the autoclave was heated to about 55 to 60 ° C. with movement. After the pressure dropped from about 10 to 2 atmospheres, an additional 160 grams of propylene was added.

The pressure then drops at a slower rate, and after about 20 hours if none further pressure drop had to be tested. the unreacted guse was drained from the autoclave These gases consisted essentially of propylene (72.5 l) with a small amount of ethylene (0.2 I ». This is probably due to the decomposition of the catalyst Lm is the catalyst / u decompose, 95 g of methanol were then put into the autoclave pumped in. 5.7 liters of gas evolved. the U consisted of more than 50% propylene. The solid mass obtained as the reaction product was washed with light gasoline and methanol and extracted cktnn.

To the resulting in Katal \ sator7crsetzung inorganic compounds / u remove suspending the polymer in diisopropyl ether and mentioned the suspension with vigorous stirring, while gaseous hydrogen chloride sä acid hindurchieitete in Hlasenform After 4 hours, even "one / a four suspension a small amount of Methanol to fill in any dissolved polymer. The polymer was tilted and separated, and dried under reduced pressure at 100 C; this gave IM) g polymer with an ash content of 0.2 "" i) the polypropylene obtained is a white, spongy, solid mass which at 140 ° C. has a transparent, rubber-like appearance and only melts above 15 ° C. X-ray diagrams showed that amorphous and crystalline fractions in the reaction product

From the liquid removed after the distillation a few grams of a very natural oil were obtained.

The product was formed into flexible sheets at 150.degree. But you can also use the product as follows fractionate: the solid polymer obtained is through hot extraction with solvents in a 1 \ tractor fractionated from the Kumagawa type and continued extraction with each solvent until the filtered solvent contained no noticeable proportions of extracted polymer.

The extracted fractions were then isolated by hot evaporation of the solvent in vacuo. The following solvents were used in succession: acetone. Diayl ether.
n-heptane.

The acetone extract consisted of oily products with low molecular weight and corresponded to 2.8 °; _{e of} the solid polymer. The ether extract corresponding to 39 °, _e de ", solid polymer consisted of a rubber-like solid product which, in solutions of tetrahydronaphthalene at 135 ° C., had an intrinsic viscosity of 1 (expressed in 100 ml / g). The obtained ether extract was examined with X-rays and found to be amorphous.

The heptane extract corresponding to 19.9% of the solid polymer consisted of a solid product which was found partially crystalline in X-ray examination (about 50%) and in solutions of Tetrahydro *

ίο naphthalene at 135 ⁰ C had a maximum viscosity of 1.2 (100 ml g).

The residue from the heptane extraction consisted of a powdery solid mass, which at about 170 C became soft and highly crystalline. as X-ray diagrams showed. He had a specific weight of about 0.92 and one in a tetrahydronaphthalene solution certain intrinsic viscosity of 3.33 (100 ml / g). I had a solution in tetrahydronaphthalene a specific viscosity of 0.374. This residue began to change at! 20 C, lost at its crystallinity was around 150 ° C and was at 170 ° C completely converted into a transparent, strongly \ iscose mass. The residue was in a flat press molded at 170 to 180 C. Plates were obtained.

the. As X-ray examinations showed, they were crystalline, an elongation of 700 ° and an elongation at break of 350 kg cm *, based on the original cross-section. The product could be hot-pressed and was strongly crystalline with an extremely high degree of hot or cold stretching Breaking Strength Fin Cold drawn thread with a For example, a diameter of 0.3 mm had a breaking strength of 32 kg mm * after stretching and an elongation of 40 ° “.

The residue exhibited properties similar to those described above, but with lower tensile strength the ether extraction, its property between those of the n-heptane extract and those of the n-heptane residue.

Example 2

15.6 g of Ahiminiumtripropyl in 530 ml of light gasoline and 2 ^× 5 g of propylene were introduced into a 2150 ml autoclave and this was heated to 70 ° C. Then 3.6 g of 1 itanetetrachloride dissolved in light gasoline were added. The temperature rose spontaneously to 95 ° C. and then fell again to 80 ° C. A further 1X g of titanium trachloride were then added. The autoclave was agitated for 4 hours while the temperature was maintained at 80 ° C. It was then cooled to 60 ° C. and the remaining gases were released 1 "Kr Polymerization catalyst was decomposed by introducing 150 ml of methanol into the autoclave. After stirring for a few minutes, the au; a solid mass existing reaction product ir methanol and light gasoline added. The product was suspended in ether and treated with hydrochloric acid to remove most of the inorganic substances. Subsequently was

So coagulated with methanol and then filtered. 20 ¹ J g of solid polymer was obtained. The purified, unfractionated polymer began to soften at Ί40 C The yield was 96 ⁰ Z ₀ , based on the eirrge led propylene, and more than 95 ° / ₀ , based on:

converted propylene.

The acrtone extract corresponded to 7.1 · »“
Polymers and consisted of oily
lower molecular weight « _f

The ether extract corresponded to 32.4 ° / ₀ of the polymer formed and consisted of a rubber-like, amorphous, solid product having an intrinsic viscosity of 0.9.

The heptane extract corresponded to 19.1% of the formed Polymers and consisted of a partially crystalline, solid mass with an intrinsic viscosity of 0.95.

The residue remaining after the extraction residue corresponded to 41.4 ° / ₀ of the polymer formed. It consisted ■ of a powdery solid product of a strongly crystalline structure, as X-ray diagrams showed, • nd had a melting point of about 180 C.

The product was pressed through a nozzle at 170 to 200.degree. The pressing was carried out by means of Nitrogen from a few atmospheres. The endless threads obtained had mechanical properties • uf, which depended on the diameter of the thread and the degree of stretching. Not from that fractionated product was obtained on pressing out at a pressure of 1 to 2 nitrogen atmospheres in the warmth threads, the nourishing properties Showed:

which showed the following mechanical properties after removal of the solvent:

diameter Book load fracture ⁵ cold of the thread on the strain stretching Initial cross-section mm based or
η % 0.6 kg / mm * 470 ίο Ο 0.25 3.5 130 150 0.1 20.5 500 0 0.05 12.7 50 300 52

Unstretched

Cold drawn
to 400 ° ₀ ....

diameter

of Thread

mm

0.5 0.2

Breaking load on the Initial average based

kg / mm ⁵

2.3 30th

Elongation at break

520
50

when from the same product the parts with lower ones Molecular weight have been eliminated. So you got a material with better mechanical properties, But it was more difficult to pull out if you didn't work at higher temperatures and at higher temperatures Pressure worked. The products with low molecular weight thus acted as plasticizers, decreased the viscosity of the mass and favored the orientation of the molecules during the expansion. .

These low molecular weight parts can also only be removed after the thread formation, for example by passing the threads through a solvent, such as ether, before or after stretching , which dissolves the low molecular weight polymers without significantly swelling the others. In this way, the processing properties of the starting product were retained, but at the same time threads were obtained. In this way, breaking loads of over 70 kg / mm ² , based on the breaking cross-section, can easily be reached. The strongly stretched thread showed exceptionally high reversible elasticity properties as well as other analogies with wool, but

The polypropylenes obtained according to the invention sit ao better mechanical properties. The spun highly crystalline polypropylene sometimes shows in the following Elongation no flow start point corresponding to a maximum in the load /

Strain.

Example 3

400 ml containing 11.4 g of aluminum triethyl

Light petrol and 291 g of a mixture of Bulen-2 and butene-1 (with a content of 70% butene-1) were placed in a 2150 ml autoclave. the The autoclave was heated to 71 ° C. and 3.6 g of titanium tetrachloride dissolved in light gasoline were added.

The temperature rose to 77 X ^1.

After 2 hours a further 3.6 g of titanium tetrachloride were added. The autoclave was on for several hours moves at temperatures between 80 and 85 C. As in the previous examples, it was

wrote, worked and obtained 86 g of a white, solid product that had a crystalline structure, as X-ray diagrams showed. The residue from the ether extraction corresponded to 46% of the polymer formed and had an intrinsic viscosity of 1.44 ml / g

measured in a solution of tetrahydronaphthalene at 135 C and a melting point of about 125 ^; C. Fibers can easily be obtained from this product by pressing in a spinning plant under nitrogen pressure at temperatures close to the softening point, which have mechanical strengths of the same order of magnitude as fibers made of polypropylene and have greater elasticity.

Claims (1)

_ ", Tungsten with organometallic compounds of the patent claims: L to mGrgppe of the periodic star obtained 1. Propylene or 1-Butene Polymers. Have as the most active catalyst components characterized in that they are compounds of titanium, in particular titanium linear -and essentially ^ are branched, a 5 tetrahalogeaide, z. B. titanium tetrachloride on the one hand and Have head-to-tail concatenation, a through-organoaluminum compound of the general see average molecular weight of more than formula "* · 20 000 and a structure corresponding to the formula r'r" AIR '"